Use of an encapsulated adhesion promoter in an aqueous adhesive joint bonding two substrates, at least one of which comprises a (tpe-pa) material

ABSTRACT

“The present invention relates to the use of an encapsulated adhesion promoter in an effective amount in an aqueous adhesive joint, said aqueous adhesive joint being intended to bond a surface of a first substrate (S1) to a surface of a second substrate (S2), at least one of said two substrates comprising a material (TPE-PA) comprising at least one thermoplastic elastomer (TPE) and/or at least one polyamide (PA), said adhesion promoter (P) comprising at least one organic molecule having at least one isocyanate function blocked by encapsulation of said organic molecule.”

FIELD OF THE INVENTION

The present invention relates to assembly, by bonding, of a firstsubstrate S1 based on a thermoplastic elastomer (abbreviated to TPE)and/or a homopolymeric or copolymeric polyamide (PA), and a secondsubstrate S2, the substrates S1 and S2 possibly being of the same natureor of a different nature.

These various possibilities for the composition of the substrate S1 andpossibly for the substrate S2 if it is of the same nature willhereinafter be denoted (TPE-PA). In addition, the term “(TPE-PA)substrate” means a substrate that comprises at least one TPE elastomeror at least one PA, or again a mixture of at least one TPE and at leastone PA.

The present invention also relates to a laminated product formed byassembling such substrates S1 and S2 by means of an aqueous adhesivejoint.

The term “aqueous adhesive joint” means a joint wherein the compositionsof primers and/or aqueous adhesives used in successive layers on the(TPE-PA) substrates comprise less than 5% of organic solvents.

The present invention also relates to a method for manufacturing such alaminate and to its use in the footwear industry, especially for themanufacture of soles and in particular for the soles of sports footwear.

One of the principal skills of the footwear industry resides in itsgreat expertise regarding bonding techniques for assembling materialswith different chemical natures and mechanical properties. This skill isparticularly important in the field of sports footwear where thematerials used, especially for the manufacture of soles, are frequentlynovel materials. This demand is multiplied by the need for theperformance generally linked to sports footwear.

During the last decade, materials based on TPE-PA, such as materialssold by the supplier Arkema under the trade name Pebax® and Rilsan®,have become more and more popular in the high end footwear field, inparticular for sports footwear, because of their mechanical propertiesand in particular their exceptional resilience properties.

Substrates formed from such polyamide block polyether copolymers,especially for the manufacture of soles for sports footwear, aregenerally assembled by bonding to other substrates using an adhesivejoint.

In general, bonding such a substrate type to produce a laminatenecessitates at least the following operations:

-   -   cleaning the surfaces of the substrates to be bonded, for        example with an organic solvent such as methylethylketone (MEK)        or with an aqueous based detergent solution;    -   applying a layer of adhesive joint, either in a solvent or in        aqueous solution, to at least the contacting surface of the        TPE-PA substrate (S1), generally using a brush; this may        optionally include application of a primer, generally in a        solvent;    -   bringing the two substrates into contact; and    -   pressing the assembly resulting from contacting.

During this bonding, both prior art primer and adhesive compositionslead to evaporation of a large quantity of organic solvent. Thus, whenmanufacturing a laminate for footwear, it is estimated that the averagequantity of adhesive used per item of footwear is 5 g and that of theprimer composition is 3 g; the solvent emission can be determined to be2.9 g per item of footwear. Assuming a production of 10 000 items offootwear per day for a production unit, the total quantity of solventgiven off by that unit is 29 kg per day.

Using an aqueous based adhesive joint can alleviate this disadvantage.Unfortunately, the degrees of adhesion and the quality of the bond,expressed as the peeling force for substrates based on TPE-PA, is farfrom being optimal for prior art laminates. Thus, with substrates formedfrom polyamide block polyether copolymer with a mean hardness of 55 to70 Shore D (for example Pebax® 55-1, Pebax® 70-1), low peeling forces inthe range from approximately 0.5 kg/cm to 3 kg/cm are obtained. However,footwear manufacturers require a peeling strength of more than 3 kg/cm.In general, aqueous adhesive joints bond with great difficulty, and inthe majority of cases do not bond at all on TPE substrates, as they havelittle or no compatibility with them.

One of the rare aqueous based adhesives that can be used to bond ontoTPE-PA substrates comprises hydrodispersible aliphatic polyisocyanates,in the form of emulsions. Examples that may be cited are hexamethylenediisocyanate, abbreviated to HDI, for example the products sold underthe trade name Desmodur® DN by the supplier Bayer. Because of their lowreactivity, said polyisocyanates cannot by themselves produce acceptabledegrees of adhesion (i.e. a peeling strength of more than 3 kg/cm) onTPE supports.

Attempts have been made to improve adhesion on (TPE-PA) substrates byincorporating polymers such as silanes into the primer or adhesiveformulations or by means of surface treatment techniques such as flametreatment, treatment with ultraviolet, corona discharge treatment,plasma treatment, or electron beam treatment.

Other techniques include chemical treatments such as, for example,attacking the substrates to be bonded using acid or basic solutions, orusing specific solvents for the materials. By way of example, metacresolis a particularly suitable solvent for polyamide based polymers. Asurface treatment with metacresol modifies the surface of the polyamidesubstrates and means that the aliphatic isocyanates can adhere moreeasily to this PA surface. However, that type of solvent (metacresol) ishighly toxic. Furthermore, that treatment can only be used in the casein which two PA substrates have to be bonded together, as metacresoldoes not act on other types of substrates.

Those acid or basic solutions or those solvents are difficult to handlebecause of their toxicity, their ecotoxicity and/or their corrosivenature. Thus, their use is frequently limited and demands suitableprotective, application and waste treatment equipment. A number ofcomplementary steps are frequently necessary, such as neutralization ofthe chemical treatments, rinsing and drying. All of those steps giverise to waste, which generates pollution. Those additional steps of theassembly procedure consume energy and reduce productivity, especiallywhen assembly is carried out on production lines.

Furthermore, when those surface treatments are complete, the substratesurface, the solidity and the mechanical properties of those substrateshave been modified.

High reactivity polyisocyanates exist; they are generally aromatic, butas they are, they cannot be dispersed in water as they are incompatiblewith water, insoluble and sensitive to water.

Latent adhesives exist comprising such high reactivity isocyanategroups, but they are deactivated by an aliphatic amine to avoid suchincompatibility problems. Such latent adhesives may be in the form ofaqueous dispersions of solid particles. The aliphatic amines react withthe isocyanate groups at the surface of such solid particles, therebycreating urea groups. Such a dispersion of particles with deactivated,and therefore non-reactive, isocyanate groups can be mixed with adispersion of molecules having polyurethane groups without riskingcross-linking, and thus form a “monocomponent” adhesive composition. Theterm “latent adhesive” is used for an adhesive that initially is appliedto a substrate and then is dried in order to evaporate all the waterfrom the adhesive, generally at low temperature in order to prevent theisocyanate functions from becoming reactive. In this manner, the surfaceof such a pre-bonded substrate is non-tacky, meaning that the substratecan be handled and stored easily. At another time (generally much laterfollowing storage, transport and/or dimensioning of the pre-bondedsubstrate), the parts comprising the pre-bonded substrate are assembledby simultaneous pressing and heat activation. During assembly bypressing, the substrates are heated to a sufficient temperature (of theorder of 60° C. to 90° C.) in order to allow the encapsulatedpolyisocyanates to become reactive. A second step for cooling thelaminate formed by the bonded substrates is then necessary.

Such a procedure for pre-bonding then hot bonding is generally employedby the automobile or furniture industry. That procedure then consists ofcontinuously applying a generally monocomponent adhesive (polyurethaneand isocyanate groups in the same composition) to a substrate using aroller.

The adhesive is then dried to evaporate off the water, but not activatedso that the polyurethane and isocyanate groups do not cross-linktogether. If drying has not been carried out in advance duringactivation, when it comes into direct contact with the isocyanates, thewater prevents or perturbs the normal cross-linking reaction of theisocyanates with the polyurethanes. The isocyanate molecules cross-linkbetween themselves (auto-cross-linking) to form a precipitate in theaqueous medium.

The substrates are then stored, for example on coils. Generally, thesecoils are then cut as a function of the geometry of the parts to bebonded. The parts are brought into contact with another substrate underpressure while simultaneously increasing the temperature to activate theadhesive (i.e. to cure it) and bond the two substrates.

In this type of bonding, the parts must be able to withstand both a highpressure and a high temperature to avoid the risk of being damaged,deteriorated or deformed; further, their mechanical properties must notbe modified.

Furthermore, such a two-step bonding process (pre-bonding then bonding)is not suitable for bonding laminates manufactured in the footwearfield. In particular, the latent bonding process described above cannotbe applied to laminates formed by materials that are both thicker andmore sensitive to heat. The parts are generally complex shapes (moldedparts) and necessitate rapid, successive bonds, which already involve alarge number of steps on a production line. Furthermore, the shape ofthe part and the materials of which it is composed means that it is notalways possible to heat the whole of the part, especially duringpressing.

Thus, the present invention aims to improve the adhesion of materialsbased on TPE-PA to aqueous adhesive joints. In particular, the inventionproposes the provision of an aqueous based adhesive composition that isready-to-use, which can bond TPE-PA substrates to any other type ofsubstrate, in order to manufacture a laminate with an improved degree ofadhesion, with a peeling resistance of more than 3 kg/cm at least.

The present invention also aims to provide a method for manufacturingsuch a laminate that is simple and easy to implement, which suffers fromnone of the disadvantages of the prior art, and in particular avoids amajor release of solvent, which has as few steps as possible in order toreduce the assembly time, and which does not deleteriously modify themechanical properties of the substrate.

The present invention also pertains to increasing the adhesion of TPE-PAmaterials with aqueous adhesive joints, thereby avoiding the use ofprimers and/or adhesives based on solvents.

The Applicant has surprisingly demonstrated that the use, in an aqueousadhesive joint, of aqueous dispersions of molecules having encapsulatedhigh reactivity isocyanate functions, allows instantaneous bonding ofsubstrates based on TPE-PA materials, and even increases the adhesion ofsaid substrates with other types of substrate.

SUMMARY OF THE INVENTION

Thus, the present invention pertains to the use of an encapsulatedadhesion promoter (P) in an effective quantity in an aqueous adhesivejoint, said aqueous adhesive joint being intended to bond a surface of afirst substrate (S1) to a surface of a second substrate (S2), at leastone (S1) of said two substrates comprising a material (TPE-PA)comprising at least one thermoplastic elastomer (TPE) and/or at leastone polyamide (PA), said adhesion promoter (P) comprising at least oneorganic molecule comprising at least two isocyanate functions blocked byencapsulation of said organic molecule.

Advantageously, said aqueous adhesive joint comprises at least one layerof aqueous primer and/or at least one layer of aqueous adhesive, saidencapsulated adhesion promoter (P) being used in said aqueous primerand/or said aqueous adhesive such that the quantity of adhesion promoter(P) represents 0.5% to 20% by weight of active substance, preferably0.5% to 10% by weight of active substance, with respect to the totaladhesive joint weight.

Advantageously, said adhesive and/or said primer are in the bicomponentform:

-   -   a first component comprising a functionalized or        non-functionalized resin, in solution or in dispersion in water,        and reactive with the isocyanate functions;    -   a second component comprising a cross-linking agent in solution        or in dispersion in water, said cross-linking agent comprising        at least one molecule having blocked or non-blocked aliphatic        isocyanate group(s) and/or at least said encapsulated adhesion        promoter (P).

Advantageously, said first component and said second component areincluded in a ready-to-use monocomponent adhesive and/or primercomposition.

Advantageously, said encapsulated adhesion promoter (P) comprises atleast one of the following aromatic organic molecules having isocyanategroups: 4,4′-methylene di(phenylisocyanate) (MDI), isophoronediisocyanate (IPDI), toluylene diisocyanate (TDI), toluylenediisocyanate-uretdione (TDI-U), TDI-urea, naphthalene-1,5-diisocyanate(NDI), 3,3′-dimethyl biphenyl-4,4′-diisocyanate (TODI) and IPDIisocyanurate (IPDI-T), and mixtures thereof.

Advantageously, said encapsulated adhesion promoter comprises at leastone TDI type and/or IPDI type aromatic isocyanate.

Advantageously, said encapsulation is carried out using at least oneencapsulating agent selected from aliphatic amines and mixtures thereof.

Advantageously, said at least one encapsulating agent is selected from:2-pentamethylene-1,5-diamine and its isomers and homologs. The term“homologs” means molecules (alkanes, alkenes, etc.) having aminefunctions, and with a similar chemical structure, containingsubstantially the same number of carbon atoms to within 1, 2 or 3 carbonatoms. Preferably, said homologs are 1,6-hexamethylene diamine,di-sec-butylamine; ethylene diamine; 1,3-propylene diamine; diethylenetriamine; triethylene tetramine;3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; methylnonane diamine;isophorone diamine; 4,4′-diaminodicyclohexylmethane; or an alkanol amineor diamine such as ethanolamine or diethanolamine; and mixtures thereof.

Advantageously, said at least one TPE is selected from COPEs and/or TPUsand/or PEBAs and/or mixtures thereof.

Advantageously, the material of substrate S1 and the material ofsubstrate S2 have the same chemical nature, i.e. substrate S1, likesubstrate S2, are based on the material TPE-PA. In this case, S2, likeS1, comprises at least one thermoplastic elastomer (TPE) or at least onepolyamide (PA) or a mixture of TPE and PA.

Advantageously, the material of substrate S1 and the material ofsubstrate S2 have different natures, S2 being selected from TPEs,homopolymers and copolymers such as polyolefins; polyamines; polyamides;polyesters; polyethers; polyesterethers; polyimides; polycarbonates;phenolic resins; polyurethanes, cross-linked or not cross-linked,especially in the form of a foam; poly(ethylene-vinyl acetate); naturalor synthetic elastomers such as polybutadienes, polyisoprenes,styrene-butadiene-styrenes (SBS), styrene-butadiene-acrylonitriles(SBN), polyacrylonitriles; natural or synthetic fabrics, especiallyfabrics formed from organic polymer fibers, such as fabrics formed frompolypropylene, polyethylene, polyesters, polyvinyl alcohol, polyvinylacetate, polyvinyl chloride or polyamide fibers; fabrics formed fromglass fibers or carbon fibers, as well as materials such as leather,paper or card; and mixtures thereof.

The present invention also pertains to a method for assembling twosubstrates S1 and S2 by bonding by means of an aqueous adhesive joint,at least one of said substrates being formed from (TPE-PA) materialcomprising at least one thermoplastic elastomer, TPE, and/or at leastone polyamide, PA, said method comprising the following order of steps:

(a) cleaning the surface of the (TPE-PA) substrate or substrates with acleaning solution;

(b) applying an aqueous adhesive joint comprising an adhesion promoteras hereinbefore defined to said surface of at least one of the twosubstrates;

(c) curing the adhesive joint at a temperature in the range 60° C. to150° C.;

(d) bringing said surface comprising the aqueous adhesive joint of oneof the substrates into contact with a surface of the other substrate toform an assembly comprising the two substrates with the aqueous adhesivejoint between them;

(e) placing the assembly in a press;

(f) and after removal from the press, recovering the assembly in theform of a laminated product.

Advantageously, step (b) for applying said adhesive joint comprises:

-   -   applying a layer of primer comprising an adhesion promoter P        based on an encapsulated highly reactive aromatic isocyanate;    -   applying a layer of bicomponent adhesive based on a low        reactivity non-blocked aliphatic isocyanate.

The present invention also pertains to a laminated product, especially asole for footwear, comprising a first substrate (S1) and a secondsubstrate (S2) adhering to each other by means of an aqueous adhesivejoint (J), said aqueous adhesive joint comprising at least oneencapsulated adhesion promoter as hereinbefore defined.

The present invention also pertains to an aqueous adhesive jointadhesion promoter for bonding a surface of a first substrate (S1) to asurface of a second substrate (S2), at least one of said substratescomprising a material (TPE-PA) comprising at least one thermoplasticelastomer (TPE) and/or at least one polyamide (PA), said adhesive jointcomprising an encapsulated adhesion promoter as hereinbefore defined.

Advantageously, said at least one TPE/PA substrate comprises at leastone material formed from amorphous or quasi-amorphous TPE and/oramorphous or quasi-amorphous polyamide. Said material preferably has anamorphous or quasi-amorphous TPE and/or amorphous or quasi-amorphouspolyamide content representing 5% to 70% by weight of the total materialweight.

Advantageously, said at least one amorphous or quasi-amorphous TPE isselected from: amorphous or quasi-amorphous COPEs and/or amorphous orquasi-amorphous TPUs and/or amorphous or quasi-amorphous PEBAs.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the present invention, an adhesion promoter (P) isused in the composition of an aqueous adhesive joint applied to asubstrate S1 based on (TPE-PA), which can augment the adhesion of saidsurface to any substrate S2 (identical to or different from substrateS1).

1—Substrate S1

The (TPE-PA) materials of substrate S1 of the invention comprise atleast one thermoplastic elastomer (TPE) and/or at least one polyamide(PA) and/or a mixture of at least one TPE and at least one PA.

The term “thermoplastic elastomer polymer (TPE)” means a block copolymercomprising alternating blocks or segments termed hard or rigid andblocks or segments termed pliable or flexible.

Examples of copolymers with hard blocks and pliable blocks that may becited are respectively (a) copolymers having polyester blocks andpolyether blocks (also termed COPE, or copolyetheresters), (b)copolymers having polyurethane blocks and polyether or polyester blocks(also termed TPU, the abbreviation for thermoplastic polyurethanes) and(c) copolymers having polyamide blocks and polyether blocks (also termedPEBA according to IUPAC).

(a) COPEs, or copolyetheresters, are copolymers with polyester blocksand polyether blocks. They are constituted by pliable polyether blocksderived from polyetherdiols and rigid polyester blocks that result fromthe reaction of at least one carboxylic diacid with at least one shortdiol chain elongation motif. The polyester blocks and polyether blocksare bonded via ester linkages resulting from the reaction of the acidfunctions of the dicarboxylic acid with the OH functions ofpolyetherdiol. The concatenation of polyethers and diacids forms thepliable blocks while the concatenation of glycol or butanediol with thediacids forms the rigid blocks of the copolyetherester. The short diolchain elongation agent may be selected from the group constituted byneopentylglycol, cyclohexanedimethanol and aliphatic glycols withformula HO(CH₂)_(n)OH wherein n is a whole number from 2 to 10.

Advantageously, the diacids are aromatic dicarboxylic acids containing 8to 14 carbon atoms. Up to 50 mole % of the aromatic dicarboxylic acidmay be replaced by at least one other aromatic dicarboxylic acidcontaining 8 to 14 carbon atoms, and/or up to 20 mole % may be replacedby an aliphatic dicarboxylic acid containing 2 to 14 carbon atoms.

Examples of aromatic dicarboxylic acids that may be cited areterephthalic, isophthalic, bibenzoic, naphthalene dicarboxylic acid,4,4′-diphenylenedicarboxylic acid, bis(p-carboxyphenyl) methane acid,ethylenebis p-benzoic acid, 1-4 tetramethylene bis(p-oxybenzoic) acid,ethylenebis(p-oxybenzoic) acid, and 1,3-trimethylenebis(p-oxybenzoic)acid.

Examples of glycols that may be cited are ethylene glycol,1,3-trimethylene glycol, 1,4-tetramethyleneglycol, 1,6-hexamethyleneglycol, 1,3-propylene glycol, 1,8-octamethyleneglycol,1,10-decamethylene glycol and 1,4-cyclohexylene dimethanol. Examples ofcopolymers having polyester blocks and polyether blocks are copolymerscontaining polyether motifs derived from polyetherdiols such aspolyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethyleneglycol (PO3G) or polytetramethylene glycol (PTMG), carboxylic diacidmotifs such as terephthalic acid and glycol (ethanediol) orbutane-1,4-diol motifs. Such copolyetheresters have been described inpatents EP 402 883 and EP 405 227. These polyetheresters arethermoplastic elastomers. They may contain plasticizers.

(b) TPUs that may be cited are polyetherurethanes that result from thecondensation of pliable polyether blocks that are polyetherdiols andrigid polyurethane blocks derived from the reaction of at least onediisocyanate that may be selected from aromatic diisocyanates (forexample MDI, TDI) and aliphatic diisocyanates (for example: HDIhexamethylenediisocyanate) with at least one short diol. The short diolchain elongation agent may be selected from the glycols cited above inthe description of the copolyetheresters. The polyurethane blocks andthe polyether blocks are bonded via linkages resulting from the reactionof the isocyanate functions with the OH functions of the polyetherdiol.

Polyesterurethanes resulting from the condensation of pliable polyesterblocks that are polyester diols and rigid polyurethane blocks derivedfrom the reaction of at least one diisocyanate with at least one shortdiol may also be cited. The polyester diols result from the condensationof carboxylic diacids advantageously selected from aliphaticdicarboxylic diacids containing 2 to 14 carbon atoms and glycols thatare short diol chain elongation agents selected from the glycols citedabove in the description of the copolyetheresters. They may containplasticizers.

(c) PEBAs result from polycondensation of polyamide blocks havingreactive ends with polyether blocks having reactive ends such as, interalia:

-   -   1) polyamide blocks having diamine chain ends with        polyoxyalkylene blocks having dicarboxylic chain ends;    -   2) polyamide blocks having dicarboxylic chain ends with        polyoxyalkylene blocks having diamine chain ends, obtained by        cyanoethylation and hydrogenation of aliphatic alpha-omega        dihydroxylated polyoxyalkylene blocks termed polyetherdiols;    -   3) polyamide blocks having dicarboxylic chain ends with        polyetherdiols; in this particular case, the products obtained        are polyetherester amides.

The polyamide blocks with dicarboxylic chain ends originate, forexample, from the condensation of polyamide precursors in the presenceof a carboxylic diacid chain limiter.

The polyamide blocks with diamine chain ends originate, for example,from the condensation of polyamide precursors in the presence of adiamine chain limiter. The number average molar mass, Mn, of thepolyamide blocks is in the range 400 to 20 000 g/mol, preferably in therange 500 to 10 000 g/mol.

The polymers with polyamide blocks and polyether blocks may also includerandomly distributed motifs.

Advantageously, three types of polyamide blocks may be used.

In the first type, the polyamide blocks originate from the condensationof a carboxylic diacid, in particular containing 4 to 20 carbon atoms,preferably containing 6 to 18 carbon atoms and an aliphatic or aromaticdiamine, in particular containing 2 to 20 carbon atoms, preferablycontaining 6 to 14 carbon atoms.

Examples of dicarboxylic acids that may be cited are1,4-cyclohexyldicarboxylic acid, and butanedioic, adipic, azelaic,suberic, sebacic, dodecanedicarboxylic or octadecanedicarboxylic acid,and terephthalic and isophthalic acids, and also dimerized fatty acids.

Examples of diamines that may be cited are tetramethylenediamine,hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine,trimethylhexamethylenediamine, isomers of bis(4-aminocyclohexyl)methane(BACM), bis(3-methyl-4-aminocyclohexyl)methane (BMACM),2-2-bis(3-methyl-4-aminocyclohexyl)propane (BMACP),para-aminodicyclo-hexylmethane (PACM), isophoronediamine (IPDA),2,6-bis(aminomethyl)norbornane (BAMN) and piperazine (Pip).

Advantageously, the blocks are PA4.12, PA4.14, PA4.18, PA6.10, PA6.12,PA6.14, PA6.18, PA9.12, PA10.10, PA10.12, PA10.14 and PA10.18.

A second type of polyamide blocks results from the condensation of oneor more alpha-omega amino carboxylic acids and/or one or more lactamscontaining 6 to 12 carbon atoms in the presence of a carboxylic diacidcontaining 4 to 12 carbon atoms or a diamine.

Examples of lactams that may be cited are caprolactam, oenantholactamand lauryllactam.

Examples of alpha-omega aminocarboxylic acids that may be cited areaminocaproic, amino-7-heptanoic, amino-11-undecanoic andamino-12-dodecanoic acid.

Advantageously the polyamide blocks of the second type are of polyamide11, polyamide 12 or polyamide 6.

A third type of polyamide blocks results from the condensation of atleast one alpha-omega aminocarboxylic acid (or a lactam), at least onediamine and at least one carboxylic diacid.

In this case, the PA blocks are prepared by polycondensation of:

-   -   linear aliphatic or aromatic diamine or diamines containing X        carbon atoms;    -   carboxylic diacid or diacids containing Y carbon atoms; and    -   comonomer or comonomers {Z} selected from lactams and        alpha-omega aminocarboxylic acids containing Z carbon atoms and        equimolar mixtures of at least one diamine containing X1 carbon        atoms and at least one carboxylic diacid containing Y1 carbon        atoms, (X1, Y1) being different from (X, Y);    -   said comonomer or comonomers {Z} being introduced in a        proportion by weight of up to 50%, preferably up to 20%, more        advantageously up to 10% with respect to the entirety of the        polyamide precursor monomers;    -   in the presence of a chain limiter selected from carboxylic        diacids.

Advantageously, the carboxylic diacid containing Y carbon atoms is usedas the chain limiter; it is introduced in excess with respect to thestoichiometry of the diamine or diamines.

In a variation of this third type, the polyamide blocks result from thecondensation of at least two alpha-omega aminocarboxylic acids or atleast two lactams containing 6 to 12 carbon atoms or a lactam and anaminocarboxylic acid not containing the same number of carbon atoms,optionally in the presence of a chain limiter.

Examples of aliphatic alpha-omega aminocarboxylic acids that may becited are aminocaproic, amino-7-heptanoic, amino-11-undecanoic andamino-12-dodecanoic acids.

Examples of lactams that may be cited are caprolactam, oenantholactamand lauryllactam.

Examples of aliphatic diamines that may be cited arehexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine.

An example of a cycloaliphatic diacid that may be cited is1,4-cyclohexyldicarboxylic acid.

Examples of aliphatic diacids that may be cited are butanedioic, adipic,azelaic, suberic, sebacic, dodecanedicarboxylic acid, dimerized fattyacids (said dimerized fatty acids preferably having a dimer content ofat least 98%; they are preferably hydrogenated; they are sold under thetrade name “PRIPOL” by the supplier “UNICHEMA”, or under the trade nameEMPOL by the supplier HENKEL) and a,w diacid polyoxyalkylenes.

Examples of aromatic diacids that may be cited are terephthalic (T) acidand isophthalic (I) acid.

Examples of cycloaliphatic diamines that may be cited are isomers ofbis(4-aminocyclohexyl)methane (BACM),bis(3-methyl-4-aminocyclohexyl)methane (BMACM), and2-2-bis(3-methyl-4-aminocyclohexyl)propane(BMACP), andpara-aminodicyclohexylmethane (PACM). The other diamines currently usedmay be isophoronediamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN)and piperazine.

Examples of polyamide blocks of the third type that may be cited are asfollows:

-   -   6.616, wherein 6.6 denotes hexamethylenediamine motifs condensed        with adipic acid. 6 denotes motifs resulting from the        condensation of caprolactam;    -   6.6/Pip.10/12, wherein 6.6 denotes hexamethylenediamine motifs        condensed with adipic acid. Pip.10 denotes motifs resulting from        the condensation of piperazine and sebacic acid. 12 denotes        motifs resulting from the condensation of lauryllactam.    -    The proportions by weight are respectively 25 to 35/20 to 30/20        to 30, the total being 80, and advantageously 30 to 35/22 to        27/22 to 27, the total being 80. For example, the proportions        32/24/24 result in a melting point of 122° C. to 137° C.;    -   6.6/6.10/11/12, wherein 6.6 denotes hexamethylenediamine        condensed with adipic acid. 6.10 denotes hexamethylenediamine        condensed with sebacic acid. 11 denotes motifs resulting from        the condensation of aminoundecanoic acid. 12 denotes motifs        resulting from the condensation of lauryllactam.    -    The proportions by weight are respectively 10 to 20/15 to 25/10        to 20/15 to 25, the total being 70, and advantageously 12 to        16/18 to 25/12 to 16/18 to 25, the total being 70.    -    As an example, the proportions 14/21/14/21 result in a melting        point of 119° C. to 131° C.

The polyether blocks may represent 5% to 85% by weight of copolymerhaving polyimide and polyether blocks. The mass Mn of the polyetherblocks is in the range 100 to 6000 g/mol, preferably in the range 200 to3000 g/mol.

The polyether blocks are constituted by alkylene oxide motifs. Thesemotifs may, for example, be ethylene oxide motifs, propylene oxidemotifs or tetrahydrofuran (which results in polytetramethylene glycolconcatenations). Thus, the following are used: PEG (polyethylene glycol)blocks, i.e. constituted by ethylene oxide motifs, PPG (propyleneglycol) blocks, i.e. constituted by propylene oxide motifs, PO3G(polytrimethylene glycol) blocks, i.e. constituted by polytrimethyleneether glycol motifs (such copolymers with polytrimethylene ether blockshave been described in patent U.S. Pat. No. 6,590,065), and PTMG blocks,i.e. constituted by tetramethylene glycol motifs also known aspolytetrahydrofuran. Advantageously, PEG blocks or blocks obtained byoxyethylation of bisphenols, such as bisphenol A, for example, are used.These latter products have been described in patent EP 613 919.

The polyether blocks may also be constituted by ethoxylated primaryamines. These blocks are also advantageously used. Examples ofethoxylated primary amines that may be cited are products with formula:

wherein m and n are in the range 1 to 20 and x is in the range 8 to 18.These products are commercially available under the trade name NORAMOX®from the supplier CECA and under the trade name GENAMIN® from thesupplier CLARIANT.

The ether motifs (A2) are, for example, derived from at least onepolyalkylene ether polyol, especially a polyalkylene ether diol,preferably selected from polyethylene glycol (PEG), polypropylene glycol(PPG), polytrimethylene glycol (PO3G), polytetramethylene glycol (PTMG)and mixtures thereof or copolymers thereof.

The pliable polyether blocks may comprise polyoxyalkylene blocks havingNH₂ chain ends, such blocks possibly being obtained by cyanoacetylationof aliphatic alpha-omega dihydroxylated polyoxyalkylene blocks known aspolyetherdiols. More particularly, it is possible to use Jeffamines (Forexample Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial productsfrom the supplier Huntsman. See also patents JP 2004346274, JP2004352794 and EP1482011).

The polyetherdiol blocks are either used as they are andco-polycondensed with the polyamide blocks having carboxylic ends, orthey are aminated in order to be transformed into polyether diamines andcondensed with the polyamide blocks having carboxylic ends. They mayalso be mixed with polyamide precursors and a diacid chain limiter inorder to produce polymers having polyamide blocks and polyether blockscontaining motifs distributed in a random manner.

Said polymers may be prepared by the simultaneous reaction of polyetherblocks and precursors of polyamide blocks; preferably, thepolycondensation is carried out at a temperature of 180° C. to 300° C.As an example, it is possible to react the polyetherdiol, polyamideprecursors and a diacid chain limiter. A polymer is obtained containingessentially polyether blocks, polyamide blocks of highly variablelength, and also various reagents that have reacted in a random mannerthat are distributed in a random (statistical) manner along the polymerchain.

It is also possible to cause the polyether diamine, polyamide precursorsand a diacid chain limiter to react. A polymer is obtained containingessentially polyether blocks, polyamide blocks of highly variablelength, but also the various reagents that have reacted in a randommanner that are distributed in a random (statistical) manner along thepolymer chain.

However, they may also advantageously be prepared by a condensationreaction of polyether blocks with polyamide blocks.

The catalyst is defined as any product that can facilitate bonding ofpolyamide blocks and polyether blocks by esterification or byamidification. The esterification catalyst is advantageously aderivative of a metal selected from the group formed by titanium,zirconium and hafnium, or a strong acid such as phosphoric or boricacid. Examples of catalysts are those described in patents U.S. Pat. No.4,331,786, U.S. Pat. No. 4,115,475, U.S. Pat. No. 4,195,015, U.S. Pat.No. 4,839,441, U.S. Pat. No. 4,864,014, U.S. Pat. No. 4,230,838 and U.S.Pat. No. 4,332,920.

The general method for preparing PEBA copolymers in two steps with esterlinkages between the PA blocks and the PE blocks is known and has beendescribed, for example, in French patent FR 2 846 332. The generalmethod for preparing the PEBA copolymers of the invention containingamide linkages between the PA blocks and the PE blocks is known and hasbeen described, for example, in European patent EP 1 482 011.

The reaction for the formation of the PA block is normally carried outat between 180° C. and 300° C., preferably in the range 200° C. to 290°C., the pressure in the reactor being established at between 5 and 30bars; it is maintained for approximately 2 to 3 hours. The pressure isslowly reduced by bringing the reactor back to atmospheric pressure,then the excess water is distilled off, for example over one or twohours.

Once the polyamide having carboxylic acid ends has been prepared, thepolyether and a catalyst are then added. The polyether may be added inone or more batches, as can the catalyst. In an advantageousimplementation, the polyether is initially added, whereupon the reactionof the OH ends of the polyether and the COOH ends of the polyamidecommences with the formation of ester bonds and the elimination ofwater. As much water as possible is eliminated from the reaction mediumby distillation, then the catalyst is introduced to complete the linkageof the polyamide blocks and the polyethylene glycol blocks. This secondstep is carried out with stirring, preferably under a vacuum of at least6 mmHg (800 Pa) at a temperature such that the reagents and thecopolymers obtained are in the molten state. As an example, thistemperature may be in the range 100° C. to 400° C., usually in the range200° C. to 300° C. The reaction is monitored by measuring the coupleexerted by the molten polymer on the stirrer or by measuring theelectrical power consumed by the stirrer. The end of the reaction isdetermined by the target value of the couple or the power.

During synthesis at the moment adjudged to be the most opportune, it isalso possible to add one or more molecules used as an antioxidant, forexample Irganox® 1010 or Irganox® 245.

The copolymers having polyamide blocks and polyether blocks may beprepared using any means that can key the polyamide blocks to thepolyether blocks. In practice, two methods are essentially employed, onebeing a two-step method, the other a one-step method.

In the two-step method, the polyamide blocks are initially manufacturedthen in a second step, the polyamide blocks are keyed to the polyetherblocks. In the one-step method, the polyamide precursors, chain limiterand polyether are mixed; a polymer containing essentially polyethyleneglycol blocks, polyamide blocks of highly variable lengths and also thevarious reagents that have reacted in a random manner which aredistributed in a random (statistical) manner along the polymer chain areobtained thereby. Irrespective of whether it is a one- or two-stepmethod, it is advantageous to operate in the presence of a catalyst. Thecatalysts described in patents U.S. Pat. No. 4,331,786, U.S. Pat. No.4,115,475, U.S. Pat. No. 4,195,015, U.S. Pat. No. 4,839,441, U.S. Pat.No. 4,864,014, U.S. Pat. No. 4,230,838 and U.S. Pat. No. 4,332,920, WO04 037898, EP 1 262 527, EP 1 270 211, EP 1 136 512, EP 1 046 675, EP 1057 870, EP 1 155 065, EP 0 506 495 and EP 0 504 058 may be used. In theone-step method, polyamide blocks are also manufactured; this is why ithas been stated at the beginning of this paragraph that the copolymerscould be prepared using any means for keying the polyamide blocks (PAblock) to the polyether blocks (PE block).

Advantageously, the PEBA copolymers have PA blocks formed from PA 6, PA11, PA 12, PA 6.12, PA 6.6/6, PA 10.10 and PA 6.14 and PE blocks formedfrom PTMG, PPG, PO3G and PEG.

(d) The polyamides are homopolyamides or copolyamides.

In accordance with a first type, the polyamides derive from thecondensation of a carboxylic diacid, in particular containing 4 to 20carbon atoms, preferably containing 6 to 18 carbon atoms, and analiphatic or aromatic diamine, in particular containing 2 to 20 carbonatoms, preferably containing 6 to 14 carbon atoms.

Examples of dicarboxylic acids that may be cited are1,4-cyclohexyldicarboxylic acid, and butanedioic, adipic, azelaic,suberic, sebacic, dodecanedicarboxylic or octadecanedicarboxylic acidand terephthalic and isophthalic acids, but also dimerized fatty acids.

Examples of diamines that may be cited are tetramethylene diamine,hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine,trimethylhexamethylenediamine, isomers of bis(4-aminocyclohexyl)methane(BACM), bis(3-methyl-4-aminocyclohexyl)methane (BMACM), 2-2-bis(3-methyl-4-aminocyclohexyl)propane (BMACP),para-aminodicyclo-hexylmethane (PACM), isophoronediamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN) and piperazine (Pip).

Advantageously, PA 4.12, PA 4,14, PA 4.18, PA 6.10, PA 6.12, PA 6.14, PA6.18, PA 9.12, PA 10.10, PA 10.12, PA 10.14 and PA 10.18 are used.

The second polyamide type results from the condensation of one or morealpha-omega aminocarboxylic acids and/or one or more lactams containing6 to 12 carbon atoms in the presence of a carboxylic diacid containing 4to 12 carbon atoms or of a diamine.

Examples of lactams that may be cited are caprolactam, oenantholactamand lauryllactam.

Examples of alpha-omega aminocarboxylic acid that may be cited areaminocaproic, amino-7-heptanoic, amino-11- undecanoic andamino-12-dodecanoic acid.

Advantageously, the polyamides of the second type are formed frompolyamide 11, polyamide 12 or polyamide 6.

A third type of polyamide results from the condensation of at least onealpha-omega aminocarboxylic acid (or a lactam), at least one diamine andat least one carboxylic diacid.

In this case, during a first step, the polyamide blocks PA are preparedby polycondensation of:

-   -   linear aliphatic or aromatic diamine or diamines containing X        carbon atoms;    -   carboxylic diacid or diacids containing Y carbon atoms; and    -   comonomer or comonomers {Z} selected from lactams and        alpha-omega aminocarboxylic acids containing Z carbon atoms and        equimolar mixtures of at least one diamine containing X1 carbon        atoms and at least one carboxylic diacid containing Y1 carbon        atoms, (X1, Y1) being different from (X, Y);    -   said comonomer or comonomers {Z} being introduced in a        proportion by weight of up to 50%, preferably up to 20%, more        advantageously up to 10% with respect to the entirety of the        polyamide precursor monomers.

Examples of aliphatic alpha-omega aminocarboxylic acids that may becited are aminocaproic, amino-7-heptanoic, amino-11-undecanoic andamino-12-dodecanoic acid.

Examples of lactams that may be cited are caprolactam, oenanthoiactamand lauryllactam.

Examples of aliphatic diamines that may be cited arehexamethylenediamine, dodecamethylenediamine andtrimethylhexamethylenediamine.

An example of a cycloaliphatic diacid that may be cited is1,4-cyclohexyldicarboxylic acid.

Examples of aliphatic diacids that may be cited are butanedioic, adipic,azelaic, suberic, sebacic or dodecanedicarboxylic acid, dimerized fattyacids (these dimerized fatty acids preferably have a dimer content of atleast 98%; they are preferably hydrogenated; they are sold under thetrade name “PRIPOL” by the supplier “UNICHEMA”, or under the trade nameEMPOL by the supplier HENKEL) and α,γ-diacid polyoxyalkylenes.

Examples of aromatic diacids that may be cited are terephthalic (T) acidand isophthalic (I) acid.

Examples of cycloaliphatic diamines that may be cited are isomers ofbis(4-aminocyclohexyl)methane (BACM),bis(3-methyl-4-aminocyclohexyl)methane (BMACM), and2-2-bis(3-methyl-4-aminocyclohexyl)propane (BMACP), andpara-aminodicyclohexylmethane (PACM). The other diamines in routine usemay be isophoronediamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN)and piperazine.

Examples of the third type of polyamide that may be cited are asfollows:

-   -   PA6.6/6, wherein 6.6 denotes hexamethylenediamine motifs        condensed with adipic acid. 6 denotes motifs resulting from the        condensation of caprolactam;    -   PA6.6/Pip.10/12, wherein 6.6 denotes hexamethylenediamine motifs        condensed with adipic acid. Pip. 10 denotes motifs resulting        from the condensation of piperazine and sebacic acid. 12 denotes        motifs resulting from the condensation of lauryllactam. The        proportions by weight are respectively 25 to 35/20 to 30/20 to        30, the total being 80, and advantageously 30 to 35/22 to 27/22        to 27, the total being 80. For example, the proportions 32/24/24        result in a melting point of 122° C. to 137° C.;    -   PA6.6/6.10/11/12, wherein 6.6 denotes hexamethylenediamine        condensed with adipic acid. 6.10 denotes hexamethylenediamine        condensed with sebacic acid. 11 denotes motifs resulting from        the condensation of aminoundecanoic acid. 12 denotes motifs        resulting from the condensation of lauryllactam. The proportions        by weight are respectively 10 to 20/15 to 25/10 to 20/15 to 25,        the total being 70, and advantageously 12 to 16/18 to 25/12 to        16/18 to 25, the total being 70. As an example, the proportions        14/21/14/21 result in a melting point of 119° C. to 131° C.

The substrate S1 is selected from the (TPE-PA) compounds defined aboveand/or mixtures thereof.

Clearly, the substrate S1 may also include additives such as catalysts,in particular based on phosphorus, UV stabilizers, dyes, nucleationagents, plasticizers, shock resistance improving agents, antioxidants,release agents, adjuvants or processing/operating auxiliaries,especially stearates such as calcium stearate, zinc stearate ormagnesium stearate, fatty acids, fatty alcohols, esters of the montanicester type, sebacic acid esters, esters of dodecanedioic acid,polyolefin waxes, amide waxes, stearamides such as ethylenebisstearamide(EBS), erucamides, fluorinated additives, especially of the DyneonDynamer FX 5914 or FX 5911 type.

Advantageously, said TPE-PA substrate comprises at least one amorphousor quasi-amorphous polymer, i.e. an adhesion promoter (A) as describedin the Applicant's French patent application FR 07/58478.

This adhesion promoter polymer is primarily amorphous. It isadvantageously selected from amorphous or quasi-amorphous compounds fromthe TPE category described above and/or from amorphous orquasi-amorphous polyamides. It may advantageously include a mixture ofthese two types of amorphous or quasi-amorphous compounds (TPE or PA).

Said at least one amorphous or quasi-amorphous TPE is preferablyselected from: amorphous or quasi-amorphous COPEs and/or amorphous orquasi-amorphous TPUs and/or amorphous or quasi-amorphous PEBAs.

Advantageously, the TPE based material that forms the substrate S1 hasan amorphous or quasi-amorphous TPE polymer content and/or amorphous orquasi-amorphous polyamide content that represents 1% to 99% by weight ofthe total weight of said material. Preferably, said content represents3% to 90% by weight of the total weight of said material. Morepreferably, this content represents 5% to 70% by weight of the totalweight of said material.

Preferably, the adhesion promoters based on amorphous or quasi-amorphouspolyamide (PA) and/or based on amorphous or quasi-amorphouspolyether-block-amide (PEBA) are used.

In accordance with a preferred implementation of the invention, thematerial of the substrate S1 is based on PEBA and further comprises anadhesion promoter polymer (A) based on amorphous or quasi-amorphous PAand/or on amorphous or quasi-amorphous PEBA.

Concerning amorphous or quasi-amorphous PAs:

In one implementation of the invention, the polyamides with motifs A1 inthe composition of the adhesion promoter (A) have a crystallinity suchthat the enthalpy of fusion during the second heating of an ISO DSC(delta Hm(2)) is less than or equal to 10 J/g, the mass being withrespect to the quantity of amide motifs contained or of polyamidecontained therein, said fusion being that of the amide motifs; finally,it may have a crystallinity (termed intermediate) such that the enthalpyof fusion during the second heating of an ISO DSC (delta Hm(2)) is inthe range 10 to 30 J/g, preferably in the range 10 and 25 J/g, the massbeing with respect to the quantity of amide motifs contained or ofpolyamide contained therein, said fusion being that of the amide motifs.Such materials are products with a behavior intermediate betweenamorphous or essentially amorphous polymers, i.e. with a second heatenthalpy of fusion in the range 0 to 10 J/g, which are no longer in thesolid state above their Tg, and genuinely semi-crystalline polymers,which are polymers that remain in the solid state, i.e. retain theirshape above their Tg. These products with intermediate behavior are thusin a more or less solid state, but are readily deformable beyond theirTg.

The term “delta Hm(2)” means the enthalpy of fusion during the secondheating of an ISO standard DSC (“Differential Scanning Calorimetry”)

The polyamides may be mainly constituted by an equimolar combination ofat least one diamine and at least one carboxylic or aromatic orcycloaliphatic diacid, the diamines being mainly cycloaliphatic, theamide motifs possibly comprising at least one other polyamide comonomerof the amino acid or lactam type or of the X,Y type (X=aliphaticdiamine, Y=aliphatic diacid).

Advantageously, the cycloaliphatic diamine or diamines may be selectedfrom bis(3-methyl-4-aminocyclohexyl)-methane (BMACM),para-aminodicyclohexylmethane (PACM), isophoronediamine (IPD),bis(4-aminocyclohexyl)methane (BACM),2,2-bis(3-methyl-4-aminocyclohexyl)propane (BMACP), and2,6-bis(aminomethyl)norbornane (BAMN).

A non-cycloaliphatic diamine may form part of the composition of theamide motif monomers (A1). Examples of non-cycloaliphatic diamines thatmay be cited are linear aliphatic diamines such as 1,4-tetramethylenediamine, 1,6-hexamethylenediamine, 1,9-nonamethylenediamine or1,10-decamethylenediamine.

The aliphatic carboxylic diacid or diacids may be selected fromaliphatic carboxylic diacids containing 6 to 36 carbon atoms, preferably9 to 18 carbon atoms, in particular 1,10-decanedicarboxylic acid(sebacic acid), 1,12-dodecanedicarboxylic acid,1,14-tetradecanedicarboxylic acid or 1,18-octadecanedicarboxylic acid.

An aromatic or cycloaliphatic carboxylic diacid may form part of thecomposition of the amide motif monomers. In this case, the carboxylicdiacid is selected from aromatic diacids, in particular isophthalic (I)acid, terephthalic (T) acid and mixtures thereof.

The alpha-omega aminocarboxylic acid or amino acid is, for example,selected from amino caproic acid, amino-7-heptanoic acid,amino-11-undecanoic acid and amino-12-dodecanoic acid.

The polyamide blocks are, for example, selected from BMACM.6, BMACM.9,BMACM.10, BMACM.12, BMACM.14, BMACM.16, BMACM.18 and mixtures thereof.

The number average molecular mass of the polyamide blocks isadvantageously in the range 500 to 12 000 g/mol, preferably in the range2000 to 6000 g/mol.

Concerning amorphous or quasi-amorphous PEBAs:

In a second implementation of the invention, an adhesion promotercopolymer (A) comprises polyamide motifs (A1) and ether block motifs(A2) and may be in the form of polyamide-polyether blocks.

The amorphous or quasi-amorphous polyamide motifs (A1) are those whichwere described in the preceding paragraph (see amorphous orquasi-amorphous PA).

As an example, the polyether block motifs (A2) are derived from at leastone polyalkylene ether polyol, especially a polyalkylene ether diol,preferably selected from polyethylene glycol (PEG), polypropylene glycol(PPG), polytrimethylene glycol (PO3G), polytetramethylene glycol (PTMG)and mixtures thereof or copolymers thereof.

The pliable polyether blocks may comprise polyoxyalkylene sequences withNH₂ chain ends, such sequences possibly being obtained bycyanoacetylation of aliphatic alpha-omega dihydroxylated polyoxyalkylenesequences known as polyetherdiols. More particularly, it is possible touse Jeffamines (For example Jeffamine® D400, D2000, ED 2003, XTJ 542,commercial products from the supplier Huntsman. See also patents JP2004346274, JP 2004352794 and EP 1 482 011).

The number average molecular mass of the polyether blocks isadvantageously in the range 200 to 4000 g/mol, preferably in the range300 to 1100 g/mol.

The adhesion promoter copolymer (A) may be prepared using the followingmethod in which:

-   -   in a first step, polyamide PA blocks are prepared by        polycondensation of:        -   diamine or diamines;        -   carboxylic diacid or diacids; and    -    if appropriate, comonomer or comonomers selected from lactams        and alpha-omega aminocarboxylic acids;        -   in the presence of a chain limiter selected from carboxylic            diacids; then    -   in a second step, the polyamide PA blocks obtained are reacted        with the polyether PE blocks in the presence of a catalyst.

The general method for preparing the copolymers of the invention in twosteps is known and has been described, for example, in French patent FR2 846 332 and in European patent EP 1 482 011.

The reaction for forming the PA block is normally carried out in therange 180° C. to 300° C., preferably in the range 200° C. to 290° C.,the pressure in the reactor being between 5 and 30 bars, and held forapproximately 2 to 3 hours. The pressure is reduced slowly, bringing thereactor back to atmospheric pressure, then the excess water is distilledoff, for example over one or two hours.

Once the polyamide having carboxylic acid ends has been prepared, thepolyether and a catalyst are then added. The polyether may be added inone or more batches, like the catalyst. In one advantageousimplementation, the polyether is added initially, whereupon the reactionof the OH ends of the polyether and the COOH ends of the polyamidecommences with the formation of ester linkages and the elimination ofwater. As much water as possible is eliminated from the reaction mediumby distillation, then the catalyst is introduced to complete the linkageof the polyamide blocks and the polyether blocks. This second step iscarried out with stirring, preferably under a vacuum of at least 15 mmHg(2000 PA) at a temperature such that the reagents and the copolymersobtained are in the molten state. As an example, this temperature may bein the range 100° C. to 400° C., usually in the range 200° C. to 300° C.The reaction is followed by measuring the couple exerted by the moltenpolymer on the stirrer or by measuring the electrical power consumed bythe stirrer. The end of the reaction is determined by the target valueof the couple or the power.

During synthesis, at a time adjudged to be opportune, it is alsopossible to add one or more molecules used as an antioxidant, forexample Irganox® 1010 or Irganox® 245.

It is also possible to consider a method for the preparation ofcopolymer (A) wherein all of the monomers are added at the start, i.e.in a single step, to carry out polycondensation of:

-   -   diamine or diamines;    -   carboxylic diacid or diacids; and    -   if appropriate, the other polyamide cornonomer or comonomers;    -   in the presence of a chain limiter selected from carboxylic        diacids;    -   in the presence of PE (polyether) blocks;    -   in the presence of a catalyst for the reaction between the        pliable PE blocks and the PA blocks.

Advantageously, the chain limiter used is said carboxylic diacid, whichis introduced in excess with respect to the stoichiometry of the diamineor diamines.

Advantageously, the catalyst used is a derivative of a metal selectedfrom the group formed by titanium, zirconium and hafnium or a strongacid such as phosphoric acid, hypophosphorous acid or boric acid.

The polycondensation may be carried out at a temperature of 240° C. to280° C.

Concerning the method for incorporating the adhesion promoter into thesolution of the substrate S1:

The adhesion promoter (A) may be introduced into the composition ofsubstrate S1 by a compounding operation or using a masterbatchcontaining the adhesion promoter polymer, or during polycondensation ofTPE, or by incorporation by dry mixing with the material based on TPEduring transformation of injection molded parts. The adhesion promotermay also be incorporated into the surface of the portion of thesubstrate to be bonded via an overmolding operation.

Advantageously, incorporation of the adhesion promoter in accordancewith the invention does not alter the intrinsic mechanical properties ofthe matrix of the substrate S1, irrespective of the method forincorporating the promoter into the substrate matrix.

2—Substrate S2

Substrate S2 may be identical to or different from substrate S1.

Substrate S2 is selected from the TPE-PA substrates defined above and/ormixture(s) thereof, homopolymers and copolymers such as polyolefins,polyamines, polyamides, polyesters, polyethers, polyesterethers,polyimides, polycarbonates, phenolic resins, polyurethanes, cross-linkedor not cross-linked, especially foams, poly (ethylene-vinyl acetate),natural or synthetic elastomers such as polybutadienes, polyisoprenes,styrene-butadiene-styrene (SBS), styrene-butadiene-acrylonitrile (SBN),polyacrylonitriles, natural or synthetic fabrics, in particular fabricsformed from organic polymer fibers, such as fabrics formed from fibersof polypropylene, polyethylene, polyesters, polyvinyl alcohol, polyvinylacetate, polyvinyl chloride, polyamide, fabrics formed from glass fibersor carbon fibers, as well as materials such as leather, paper or board.

3—Cleaning Solutions

The solutions for cleaning the surface of the substrates to be bondedare those generally used to eliminate impurities, fats, or foreignagents that may alter the adhesion of the primers and/or the adhesiveson the substrates.

These cleaning solutions may also contain additives such as wettingagents or detergents to encourage the elimination of pollutingsubstances and/or to improve the wettability of the supports.

Examples that may be cited are water-based cleaning solutions, solutionsbased on aliphatic organic solvents or solutions based on aromaticsolvents and mixtures thereof composed of 2 or more than 3 of the abovesolvents.

The principal groups of solvents are:

-   -   water;    -   ketones (for example: acetone, methylethylketone);    -   alcohols (for example: methanol, ethanol, isopropanol, glycols);    -   esters (for example: acetates, agro-solvents);    -   ethers (for example: ethyl ethers, THF, dioxane);    -   glycol ethers;    -   aromatic hydrocarbons (benzene, toluene, xylene, cumene);    -   petroleum solvents (apart from aromatics: alkanes, alkenes);    -   halogenated hydrocarbons: (chlorinated, brominated or        fluorinated);    -   particular solvents (amines, amides, terpenes).

The organic solvents or solutions based on water and/or based on organicsolvents are carefully selected in order to reduce solvent emissions asmuch as possible, and to reduce the risks linked to toxicity andecotoxicity. Advantageously, the organic type cleaning solvent selectedis methylethylketone (MEK,) or an aqueous based detergent solution(dispersion or emulsion).

The cleaning method may be carried out using techniques that are inroutine use in the field, such as: brush application, spraying,immersion, etc. The preferred technique for cleaning a (TPE-PA)substrate is immersion as it ensures homogeneity of the effects ofadhesion promotion as well as a uniform degree of bonding. Cleaning byimmersion can most easily avoid contamination of the substrate by anyimpurities. Furthermore, the immersion technique is perfectly adapted tocontinuous bonding methods on an assembly line. Alternatively, cleaningwith a brush or using a textile may be employed, but it generates soiland waste.

Next, the cleaned surface is “dried” at a temperature in the range 50°C. to 140° C., in order to be able to apply the adhesive joint directlyto the cleaned surface; said adhesive joint may, for example, comprise afirst layer of primer and a layer of adhesive applied to said firstlayer of primer.

4—Adhesive Joint (J)

In general, the substrates (S1) based on (TPE-PA) are assembled bybonding with other substrates (S2) by means of an adhesive joint. Theadhesive joint may be applied in one or more layers of adhesive(s) withdifferent compositions or otherwise to at least one of the surfaces ofthe substrates to be bonded. The adhesive joint may further comprise afirst layer of primer, applied to one substrate before application ofthe layer(s) of adhesive, in order to improve wetting of the surface ofthe substrate by the adhesive. The adhesive and the primer may havecompositions that may or may not be alike, the primer usually having aviscosity that is lower than that of the adhesive. One of the advantagesof the invention is that both the adhesion primer(s) and the adhesive(s)used are mainly aqueous.

-   -   Concerning the adhesives applied to the substrate(s) based on        (TPE-PA):

The adhesives used may be monocomponent containing, for example, apolymer (functionalized or not) and a cross-linking agent in the samedispersion in water. The adhesives may also be multicomponent adhesives.They are usually bicomponent adhesives comprising a first component thatmay or may not be a functionalized resin (for example hydroxylated,carboxylated, epoxy, amine, amide, etc.), in dispersion or in solutionin an organic solvent and/or in water, and a second component(cross-linking agent) such as a solution of isocyanate in an organicsolvent or a pure isocyanate or a dispersion of isocyanate in water. Inorder to limit solvent emission, the bonding method of the inventionpreferably employs aqueous solutions.

Clearly, other types of aqueous based adhesive may be used. As anexample, “contact” adhesives may be used, which act by fusion of the twolayers in contact.

-   -   Concerning the primers applied to the (TPE-PA) based substrates:

Monocomponent or multicomponent primer compositions may be used in thepresent invention. The preferred primers for use in the presentinvention are generally bicomponent compositions wherein the firstcomponent is a rein (functionalized or otherwise) in solution in anorganic solvent or in an aqueous solvent or in dispersion in an aqueoussolvent, and the second component (cross-linking agent), which is addedto the first component just before use of the primer, is an isocyanateor a mixture of isocyanates, also in solution in an organic solvent orin an aqueous solvent or in dispersion in an aqueous solvent.

Depending on the composition of the solvent for said primers, this stepfor application of the primer thus involves more or fewer emissions oforganic solvents into the atmosphere. Preferably, then, the bondingmethod of the invention employs aqueous solutions. Clearly, any othercross-linking agent may be used, for example hexamethoxymethylmelamine(HMMM), which is appropriate in the case of primers containing water.

5—Adhesion Promoter

Said adhesion promoter of the invention comprises at least one organicmolecule comprising one or more highly reactive isocyanate groups (orfunctions) (I). Said molecule is encapsulated, or at least its highlyreactive isocyanate groups are.

The term “molecules having highly reactive isocyanate groups that canform part of the composition of the adhesion promoter of the invention”means any diisocyanates and polyisocyanates that are solid at ambienttemperature, with a melting point of more than 40° C., and available inthe form of a powder with a mean particle size of less than 200 μm,preferably less than 100 μm. Said molecules having isocyanate groups ofthe present invention may be aliphatic, cycloaliphatic, heterocyclic oraromatic.

Preferably, the molecules having highly reactive isocyanate groups ofthe present invention are aromatic molecules.

Particularly appropriate examples of molecules having highly reactiveisocyanate functions for use in the composition of the adhesion promoterof the invention that may be cited are: 4,4′-methylenedi(phenylisocyanate) (=diphenylmethane-4,4′-diisocyanate, MDI),isophorone diisocyanate (IPDI), 2,4-toluene diisocyanate (TDI),toluylene diisocyanate-uretdione (=TDI-uretdione, TDI-U, dimeric1-methyl-2,4-phenylene diisocyanate), TDI-urea,naphthalene-1,5-diisocyanate (NDI), 3,3′-dimethylbiphenyl-4,4′-diisocyanate (TODI) and IPDI isocyanurate (IPDI-T), andmixtures thereof.

Preferably, 2,4-toluene diisocyanate (TDI) or the trimer of isophoronediisocyanate (IPDI) is used.

Said molecules are encapsulated by reacting the isocyanates withaliphatic amines to form urea functions. In addition, in accordance withthe invention, the term “organic molecules having isocyanate function(s)blocked by encapsulation” means solid, very finely milled particlescomprising molecules having isocyanate functions (I) deactivated byaliphatic amines, which thereby create a protective layer or capsulecomprising urea functions on the surface of said solid particles.

Examples of aliphatic amines forming an agent encapsulating theisocyanates as described above that may be cited are:2-pentamethylene-1,5-diamine and its isomers and homologs such as, forexample, 1,6-hexamethylene diamine, di-sec-butylamine; ethylene diamine;1,3-propylene diamine; diethylene triamine; triethylene tetramine;3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; methylnonane diamine;isophorone diamine; 4,4′-diaminodicyclohexylmethane; or an alkanol-amineor -diamine, such as ethanolamine or diethanolamine.

Preferred aliphatic amines that may be used are 2-pentamethylene-1,5-diamine and its isomers and homologs such as, forexample, 1,6-hexamethylene diamine.

Because of this encapsulation, the isocyanate groups are deactivated,i.e. they are not reactive with other molecules. Said encapsulationprevents the isocyanate functions from reacting with each other or withother molecules such as water, resins (polyurethanes) and othermolecules that might react with the isocyanate functions.

The adhesion promoter of the invention comprising such molecules may beincorporated in aqueous dispersion and/or mixed with resins, inparticular polyurethanes, to form a monocomponent adhesive.

In accordance with the invention, the adhesion promoter is preferablyincorporated into the aqueous primer and/or the aqueous adhesive that isintended to come into contact with the TPE-A support in an amount of0.5% to 20% by weight of active substance, preferably in the range 0.5%to 10% by weight of the active substance with respect to the total massof primer and/or adhesive.

The adhesion promoter is “activated” during the operation for curing,also termed drying, the primer or the adhesive at a temperature in therange 50° C. to 140° C., preferably in the range 70° C. to 120° C. Thisactivation is carried out directly after applying the primer or theadhesive to the substrate, without necessitating an intermediate stepfor evaporation of water, and it precedes bringing the substrates intocontact using the press.

During thermal activation, the protective capsule comprising the surfaceurea functions opens up and releases the isocyanate functions, whichmeans that they can react both with the chemical functions available onthe surface of the (TPE-PA) substrates and with any other components ofthe adhesives; they thus act as the adhesion promoter.

Such organic molecules having isocyanate function(s) blocked byencapsulation are available in the solid state or in the pre-dispersedstate. In this latter case, dispersion agents, wetting agents orviscosity modifying agents may be introduced to provide the dispersionswith stability.

These organic molecules having isocyanate function(s) blocked byencapsulation are, for example, commercially available from the supplierBayer Material Science under the trade name Dispercoll BL XP 2514(deactivated TDI dimer) and Desmodur LP BUEJ 471 or Desmodur Z XP 2589(deactivated IPDI trimer).

Encapsulated TDI type polyisocyanates are preferably used.

The adhesion promoter of the invention may be used alone or incombination with one (or more) other isocyanate(s), blocked or notblocked, encapsulated or not encapsulated, in order to control thereactivity and the physico-chemical properties of the adhesive joint.

Bonding onto TPE-PA supports requires highly reactive adhesives.However, adhesives based on highly reactive isocyanates form very rigidlayers, which cannot readily withstand the deforming loadings linked tosports footwear.

In a preferred embodiment of the present invention, the following areapplied in succession to the surface of a substrate:

-   -   a layer of primer comprising an adhesion promoter based on an        encapsulated highly reactive aromatic isocyanate;    -   a layer of conventional bicomponent adhesive (based on a low        reactivity, non-blocked aliphatic isocyanate).

Thus, after activation, the primer forms a highly reactive adhesionlayer with the substrate surface. Since the layer of primer is frangibleon bending, a very thin layer of primer is sufficient.

Because of its great affinity for the primer, the adhesive provides theadhesion proper. The layer of adhesive is in itself highly flexible.

In accordance with another embodiment, molecules with non-blockedisocyanate groups are mixed into the composition of the primer and/orthe adhesive with molecules having encapsulated isocyanate groups of theadhesion promoter of the invention. Using a promoter according to theinvention in existing primer and/or adhesive compositions (monocomponentor multi component) means that the compromise between adhesion to TPE-PAsubstrates and pliability of the adhesive joints and the laminatesobtained can be adjusted. The encapsulated highly reactive isocyanatesprovide adhesion to the TPE-PA material, while the non-blocked and lowreactivity isocyanates on the TPE-PA ensure cross-linking of theadhesive as well as the chemical hold and pliability of the adhesivejoint obtained.

According to the present invention, it has been shown that,surprisingly, the adhesion promoter could readily be used without theneed for a prior step for evaporating off the water from the adhesivejoint before bonding. As a result, bonding is carried out directly afterapplying the adhesive.

The method of the invention also means that encapsulated aromaticisocyanates and non-blocked aliphatic isocyanates can be used in asynergistic manner, in contrast to the existing method for latentadhesives.

The method of the invention allows an adhesion promoter to beincorporated into the primer or into the adhesive or both into theprimer and into the adhesive. In this latter case, the affinity betweenthe adhesive and the primer is improved.

Preferably, the adhesion promoter of the present invention is used inthe portion of the adhesive joint that is applied directly to thesubstrate surface, i.e. in the primer or in the adhesive if no primer isused.

Clearly, these preferred embodiments of the present invention do notexclude other possibilities for using the adhesion promoter in theadhesive joint, such as using it in the adhesive but not in theintermediate primer between the substrate and the adhesive.

6—Method for Manufacturing a Laminate

The present invention also concerns a method for manufacturing alaminate. In accordance with the present invention, bonding of the typesdescribed of substrates (S1) onto substrates (S2) for the manufacture oflaminates comprises the steps described below.

In accordance with a first advantageous implementation in the case inwhich substrates S1 and S2 are formed from (TPE-PA) that may or may notbe of the same nature, the method for manufacturing a laminatecomprises:

(a) cleaning surfaces S1and S2 with a cleaning solution;

(b) drying at a temperature in the range 20° C. to 120° C.;

(c) optionally, applying a layer of aqueous based primer comprising thepromoter of the invention to S1 and/or S2;

(d) curing the primer layer(s) if necessary at a temperature in therange 60° C. to 150° C. for 5 minutes, to activate the isocyanate groupsof the promoter;

(e) applying at least one layer of aqueous based adhesive onto a surfaceof at least one of the two substrates and/or onto the surface of theprimer layer(s) if already deposited on S1 and/or S2.

During said step (e), said adhesive comprises the adhesion promoter ofthe invention in the case in which no primer has already been applied;or in the case in which a primer with no adhesion promoter has beenapplied. In the case in which a primer comprising an adhesion promoterof the invention has already been applied in step (c), said adhesive mayoptionally also comprise an adhesion promoter according to theinvention, for greater affinity with the primer and thus greateradhesion efficacy;

(f) curing the layers of adhesives at a temperature of the order of 60°C. to 150° C. for 5 minutes to activate the adhesion promoter;

(g) as soon as activation of the surface comprising the layer of aqueousadhesive of one of the substrates is complete, bringing it into contactwith the surface, which may or may not comprise a layer of adhesive, ofthe other substrate;

(h) pressing the assembly; then removing from the press;

(i) recovering the laminated product.

The pressure applied during the pressing step is in the range 1 to 15kg/cm², preferably in the range 3 to 10 kg/cm².

Pressing may be carried out in a humid atmosphere with the air having arelative humidity HR³ of more than 5%, preferably more than 10%, morepreferably more than 20%.

In accordance with a second advantageous implementation of the presentinvention, in the case in which S1 is formed from (TPE-PA) and thechemical nature of S2 is other than (TPE-PA), the method formanufacturing a laminate comprises:

(a) cleaning the surface S1 with a cleaning solution;

Cleaning and/or preparation of substrate S2 is adapted to the nature ofthe substrate and uses normal techniques that are known to the skilledperson;

(b) drying S1 at a temperature in the range 20° C. to 140° C.;

(c) optional (i.e. non essential) application of a layer of aqueousbased primer to S1 followed, if appropriate, by curing said primer, saidprimer comprising an adhesion promoter according to the invention;

(d) applying or not applying a layer of an appropriate primer to thesubstrate S2 followed, if appropriate, by curing said primer;

(e) applying a layer of aqueous based adhesive to the surface of S1 orto the surface of the primer that may already have been deposited on S1,said adhesive comprising the adhesion promoter according to theinvention in the case where no primer has already been applied, or inthe case in which a primer with no adhesion promoter has been applied.In the case in which a primer comprising an adhesion promoter accordingto the invention has already been applied in step (c), said adhesive mayoptionally also comprise an adhesion promoter according to theinvention, for greater affinity with the primer and thus greateradhesion efficiency;

(f) curing the layer of adhesive at a temperature of the order of 60° C.to 150° C.;

(g) applying a layer of adhesive to the surface of S2 or to the surfaceof the primer if it has already been deposited on S2. Said adhesive ispreferably aqueous and compatible with the adhesive deposited on thesubstrate S1. Advantageously, said adhesive is identical to thatdeposited on the substrate S1;

(h) curing the adhesive. If it is the same adhesive as with step (f),curing is carried out at the same temperature as in (f). If it isanother adhesive, the curing temperature is a function of the supportand the recommendations of the formulator;

(i) bringing the surface comprising the layer of activated aqueousadhesive of substrate S1 into contact with the surface comprising thelayer of activated adhesive of substrate S2;

(j) pressing the assembly; then removing it from the press;

(k) recovering the laminated product.

The pressure applied during the pressing step is in the range 1 to 15kg/cm², preferably in the range 3 to 10 kg/cm².

Pressing may be carried out in a humid atmosphere, the air having arelative humidity HR³ of more than 5%, preferably more than 10% and morepreferably more than 20%.

The presses used in the method of the invention are presses that areconventional in the laminate manufacturing field.

When applied to the manufacture of laminates, incorporating an adhesionpromoter into the primer and/or into the adhesive of the presentinvention thus means that a method can be used that is both:

-   -   reliable, meaning that adhesion of (TPE-PA)s with aqueous        adhesive joints is improved; and    -   safe, since a completely aqueous adhesive joint (adhesive and/or        primer included) is used.

According to an advantageous implementation of the invention, thesurfaces of the substrates to be bonded are cleaned with an aqueousbased detergent solution, the adhesive used is aqueous, along with anyprimer used, such that solvent emission during the course of the methodof the invention is considerably reduced.

EXAMPLES

The following examples illustrate the present invention without limitingits scope. In the examples, unless otherwise indicated, all of thepercentages and portions are expressed by weight.

Substrates:

PEBAX® 5533: type PA12-PTMG PEBA (polyamide 12-polytetramethyleneglycol), grade PEBAX® 5533 SP01 in the tables, sold by the supplierARKEMA.

PEBAX® 7033: type PA12-PTMG PEBA (polyamide 12-polytetramethyleneglycol), sold by the supplier ARKEMA.

PEBAX® 7033 is harder than PEBAX® 5533

Geometry of Substrates:

Width: 15 mm;

Length: 100 mm;

Thickness: 1 mm.

In the following examples, the layer of primer had a thickness (aftercuring) of 1 to 30 μm and the layer of adhesive had a thickness (aftercuring) of 30 to 50 μm.

Adhesion Promoter:

Dispercoll® BL XP 2514: aromatic dimeric TDI type isocyanate deactivatedby encapsulation, sold by the supplier Bayer Material Science.

Cleaning Solution:

MEK: METHYL ETHYL KETONE (synonym: 2-butanone).

Primers:

W104: aqueous based primer sold by the supplier DONGSUNG under the tradename “Aquace® W104” (dry extract−30 min at 150° C.=40% by weight ofpolyurethane);

ARF 40: aliphatic cross-linking agent: ARF-40® sold by the supplierDONGSUNG. (Dry extract−30 min at 150° C.=83.5% by weight ofpolyisocyanate);

Dply 171-2: solvent base primer sold by the supplier DONGSUNG under thetrade name “D-Ply® 171-2” (dry extract−30 min at 150° C.=10% by weight).

RFE® cross-linking agent sold by the supplier Bayer: solution oftris(p-isocyanatophenyl) thiophosphate in ethyl acetate (dry extract−30min at 150° C.=26.9% by weight in ethyl acetate).

Adhesive:

W01: aqueous adhesive sold by the supplier DONGSUNG under the trade name“Aquace® W01”: Solution of modified polyurethane in MEK+ethyl acetatesolvent (dry extract−30 min at 150° C.=46.9% by weight of polyurethane);

ARF 40: ARF-40® cross-linking agent sold by the supplier DONGSUNG. (dryextract−30 min at 150° C.=83.5% by weight of polyisocyanate).

Equipment:

The tests were carried out using the following equipment:

-   -   hydraulic press (8 to 15 kg/cm²);    -   Heraeus convection oven set at 70° C., ventilated;    -   ISO 34 punch;    -   Pneumatic press to cut specimens.

General Operational Assembly Mode:

Examples:

Preparation of Substrate (S1)

-   -   cleaning solution: MEK;    -   cleaning with cloth or immersing a smooth face of substrate S1,        cleaning time: 3 to 20 s;    -   drying for 5 minutes at temperatures in the range 20° C. to 120°        C.;    -   application of an aqueous primer (except in the case of the        examples of the invention Nos: 26 and 27) using a brush.    -    The aqueous primer comprised a first component and a second        component. In the tests shown in the various tables, the second        component corresponded to 5% by weight of cross-linking agent        with respect to the total primer weight. This second component        corresponded either to ARF-40® for comparative tests Nos: 1, 2,        3, 4, 5, 6, and 7 or to Dispercoll BL XP 2514 for the examples        of the invention, Nos: 10, 11, 12, 13, 14, 15, 16, 17, 18 and        22;    -   curing for 5 minutes at 60° C. to 150° C. in a ventilated oven;    -   cooling for 2 minutes to ambient temperature;    -   application of aqueous adhesive using a brush.    -    Similarly, in these tests, the aqueous adhesive comprised a        first component and a second component. In the tests shown in        the various tables, the second component corresponded to 5% by        weight of cross-linking agent with respect to the total primer        weight. This second component corresponded to ARF-40® for tests        Nos: 1 to 25 or Dispercoll BL XP 2514 for the examples according        to the invention Nos: 26 and 27 which included an adhesive with        an adhesion promoter according to the invention;    -   curing: 5 minutes at 70° C. in a ventilated oven, except for the        examples of the invention Nos: 26 and 27.    -   Preparation of Substrate (S2)

In the case in which the substrate S2 is of a (TPE-PA) nature and theprimer used is an aqueous based primer, the preparation of substrate S2is identical to that of the substrate S1 defined in the precedingparagraph entitled: Preparation of support S1.

In the case in which the substrate S2 is of a (TPE-PA) nature and theprimer is solvent based, the preparation of the substrate S2 is asfollows:

-   -   cleaning a smooth face of the substrate S2 with MEK solvent;    -   cleaning time 3 s to 20 s;    -   drying for 2 minutes at ambient temperature;    -   applying primer Dply 171-2 (+5% of RFE® cross-linking agent)        using a brush;    -   drying for 5 minutes at 70° C. in a ventilated oven;    -   cooling for 2 minutes to ambient temperature;    -   applying adhesive W01 (+5% of ARF-40® cross-linking agent) using        a brush;    -   drying for 5 minutes at 70° C. in a ventilated oven.

Peeling Tests

Adhesion of the substrates is directly linked to the values for thepeeling forces.

A peeling test in accordance with International standard ISO 11339 wascarried out on the laminates of each of tests Nos 1 to 27 at a speed of100 mm/minute. The peeling tests were preferably carried out during aperiod in the range 2 hours to 48 hours after bonding.

The results of the various tests are shown in Tables 1 to 4.

The results show that irrespective of the hardness of the Pebax® used,high peeling resistances of well over 3 kg/cm were obtained because ofthe method for manufacturing the laminates of the invention. Theadhesion results were optimized with peeling forces of more than 8,especially for laminates wherein the two substrates were (TPE-PA) based,and for activation temperatures (curing) of the order of 90° C. or 100°C. for even better adhesion.

Using an adhesion promoter in the adhesive joint of the invention doesnot necessitate a specific prior step for evaporating water. The twosubstrates may be brought into contact directly after rapid thermalactivation (approximately 5 minutes) of the layer of the adhesive jointapplied to at least one of the substrates. Contacting is carried out ina press at ambient temperature.

Table 1 shows the peeling force results for various tests carried out onPebax® 5533 substrates and on Pebax® 7033 substrates with primers withno adhesion promoter (ARF 40) or with an adhesion promoter (DispercollBL XP 2514) for activation temperatures (curing) of the primer of 90° C.or 100° C.

Examples Nos: 10, 14 and 18, 22 in accordance with the inventionexhibited regular adhesion and a degree of adhesion that was higher thanthat of the corresponding comparative tests (tests Nos: 2, 3 and 5, 6respectively) which did not use the adhesion promoter of the presentinvention in the primer.

The adhesion results were further improved with activation temperaturesof 100° C.

Comparison of the examples of the invention No: 10 of Table 1 and No: 11of Table 2:

On amorphous Pebax/Pebax substrates, the adhesion efficiency of theadhesion promoter in the primer was decoupled because of the presence ofamorphous PEBA. Note in this regard the synergistic effect of theadhesion promoter in the adhesive joint of the present invention and ofthe adhesion promoter (amorphous PEBA) in the PEBA material, as definedin French patent application No: 07/58478.

The greater the weight ratio of the amorphous PEBA (5%, 10%, 15%) in thePEBA substrate, the greater the adhesion efficacy (peeling force morethan 7 kg/cm).

The examples of the invention Nos: 12, 13, 26 and 27 of Table 2 exhibita peeling force of more than 6 or 7 kg/cm, irrespective of the mode ofincorporation of the adhesion promoter of the invention: either into theprimer or into the adhesive (with no prior primer layer) in theseexamples.

Tables 3 and 4 demonstrate that an increase in the activationtemperature (100° C. instead of 90° C.) caused an increase in the degreeof adhesion (peeling forces of more than 8 or 10 kg/cm in all cases).

Table 4 shows that, compared with adhesion on a pure Pebax® 7033substrate (Examples 18 and 22), the degree of adhesion with an adhesionpromoter of the invention on a Pebax® 7033/amorphous PEBA substrate ismultiplied due to the synergistic effect of the “amorphous PEBA”promoter (A) as defined in French patent application No: 07/58478 andthe promoter (P) of the invention.

TABLE 1 Peeling Primer test curing Peeling Primer II temper- Force NoSupport S1 Cleaning Primer I ARF40% BL XP ature Adhesive Adhesive PrimerCleaning Support S2 Kg/cm Remarks 1 Pebax ® MEK Aquace 5% —  70° C.Aquace Aquace DPLY MEK Pebax ® 0.5 to 1.0 Irregular 5533 W104 W01 W01171-2 5533 adhesion 2 Pebax ® MEK Aquace 5% —  90° C. Aquace Aquace DPLYMEK Pebax ® 0.5 to 1.0 Irregular 5533 W104 W01 W01 171-2 5533 adhesion 3Pebax ® MEK Aquace 5% — 100° C. Aquace Aquace DPLY MEK Pebax ® 0.5 to1.0 Irregular 5533 W104 W01 W01 171-2 5533 adhesion 10 Pebax ® MEKAquace — 5%  90° C. Aquace Aquace DPLY MEK Pebax ® >5.0 Regular 5533W104 W01 W01 171-2 5533 adhesion 14 Pebax ® MEK Aquace — 5% 100° C.Aquace Aquace DPLY MEK Pebax ® >8.0 Regular 5533 W104 W01 W01 171-2 5533adhesion 4 Pebax ® MEK Aquace 5% —  70° C. Aquace Aquace DPLY MEKPebax ® 0.5 to 1.0 Irregular 7033 W104 W01 W01 171-2 5533 adhesion 5Pebax ® MEK Aquace 5% —  90° C. Aquace Aquace DPLY MEK Pebax ® 0.5 to1.0 Irregular 7033 W104 W01 W01 171-2 5533 adhesion 6 Pebax ® MEK Aquace5% — 100° C. Aquace Aquace DPLY MEK Pebax ® 0.5 to 1.0 Irregular 7033W104 W01 W01 171-2 5533 adhesion 18 Pebax ® MEK Aquace — 5%  90° C.Aquace Aquace DPLY MEK Pebax ® >4.0 Regular 7033 W104 W01 W01 171-2 5533adhesion 22 Pebax ® MEK Aquace — 5% 100° C. Aquace Aquace DPLY MEKPebax ® >4.0 Regular 7033 W104 W01 W01 171-2 5533 adhesion

TABLE 2 Peeling Primer test Primer II curing Peeling Dispercoll temper-Force No Support S1 Cleaning Primer I ARF40%

ature Adhesive Adhesive Primer Cleaning Support S2 Kg/cm Remarks 7Pebax ® MEK Aquace 5% — 90° C. Aquace Aquace DPLY MEK Pebax ® >5.0Regular 5533/ W104 W01 W01 171-2 5533 adhesion amorphous Pebax ratio95/5 11 Pebax ® MEK Aquace — 5% 90° C. Aquace Aquace DPLY MEKPebax ® >6.0 Regular 5533/ W104 W01 W01 171-2 5533 adhesion amorphousPebax ratio 95/5 12 Pebax ® MEK Aquace — 5% 90° C. Aquace Aquace DPLYMEK Pebax ® >7.0 Regular 5533/ W104 W01 W01 171-2 5533 adhesionamorphous Pebax ratio 90/10 26 Pebax ® MEK — — — — Aquace Aquace DPLYMEK Pebax ® >6.0 Regular 5533/ W01 + W01 171-2 5533 adhesion amorphous5%* Pebax dispercoll ratio 90/10 BLXP 2514 13 Pebax ® MEK Aquace — 5%90° C. Aquace Aquace DPLY MEK Pebax ® >7.0 Regular 5533/ W104 W01 W01171-2 5533 adhesion amorphous Pebax ratio 85/15 27 Pebax ® MEK — — — —Aquace Aquace DPLY MEK Pebax ® >7.0 Regular 5533/ W01 + W01 171-2 5533adhesion amorphous 5%* Pebax dispercoll ratio 85/15 BLXP 2514

indicates data missing or illegible when filed

TABLE 3 Peeling Primer test Primer II curing Peeling Dispercoll temper-Force No Support S1 Cleaning Primer I ARF40%

ature Adhesive Adhesive Primer Cleaning Support S2 Kg/cm Remarks 15Pebax ® MEK Aquace — 5% 100° C. Aquace Aquace DPLY MEK Pebax ® >10.0Regular 5533/ W104 W01 W01 171-2 5533 adhesion amorphous Pebax ratio95/5 16 Pebax ® MEK Aquace — 5% 100° C. Aquace Aquace DPLY MEKPebax ® >10.0 Regular 5533/ W104 W01 W01 171-2 5533 adhesion amorphousPebax ratio 90/10 17 Pebax ® MEK Aquace — 5% 100° C. Aquace Aquace DPLYMEK Pebax ® >10.0 Regular 5533/ W104 W01 W01 171-2 5533 adhesionamorphous Pebax ratio 85/15

indicates data missing or illegible when filed

TABLE 4 Peeling Primer test Primer II curing Peeling Dispercoll temper-Force No Support S1 Cleaning Primer I ARF40%

ature Adhesive Adhesive Primer Cleaning Support S2 Kg/cm Remarks 19Pebax ® MEK Aquace — 5%  90° C. Aquace Aquace DPLY MEK Pebax ® >5.0Regular 7033/ W104 W01 W01 171-2 5533 adhesion amorphous Pebax ratio95/5 23 Pebax ® MEK Aquace — 5% 100° C. Aquace Aquace DPLY MEKPebax ® >8.0 Regular 7033/ W104 W01 W01 171-2 5533 adhesion amorphousPebax ratio 95/5 20 Pebax ® MEK Aquace — 5%  90° C. Aquace Aquace DPLYMEK Pebax ® >6.0 Regular 7033/ W104 W01 W01 171-2 5533 adhesionamorphous Pebax ratio 90/10 24 Pebax ® MEK Aquace — 5% 100° C. AquaceAquace DPLY MEK Pebax ® >8.0 Regular 7033/ W104 W01 W01 171-2 5533adhesion amorphous Pebax ratio 90/10 21 Pebax ® MEK Aquace — 5%  90° C.Aquace Aquace DPLY MEK Pebax ® >7.0 Regular 7033/ W104 W01 W01 171-25533 adhesion amorphous Pebax ratio 85/15 25 Pebax ® MEK Aquace — 5%100° C. Aquace Aquace DPLY MEK Pebax ® >10.0 Regular 7033/ W104 W01 W01171-2 5533 adhesion amorphous Pebax ratio 85/15

indicates data missing or illegible when filed

1. A laminated product comprising an encapsulated adhesion promoter (P)in an effective quantity in an aqueous adhesive joint, said aqueousadhesive joint bonding a surface of a first substrate (S1) to a surfaceof a second substrate (S2), at least one of said two substratescomprising a material (TPE-PA) comprising at least one thermoplasticelastomer (TPE) and/or at least one polyamide (PA), said adhesionpromoter (P) comprising at least one organic molecule comprising atleast two isocyanate functions block by encapsulation of said organicmolecule.
 2. The laminated product as claimed in claim 1, wherein saidaqueous adhesive joint comprises at least one layer of aqueous primerand/or at least one layer of aqueous adhesive, said encapsulatedadhesion promoter (P) being used in said aqueous primer and/or saidaqueous adhesive such that the quantity of adhesion promoter (P)represents 0.5% to 20% by weight of active substance with respect to thetotal adhesive joint weight.
 3. The laminated product as claimed inclaim 2, wherein said adhesive and/or said primer are in the bicomponentform: a first component comprising a functionalized ornon-functionalized resin, in solution or in dispersion in water, andreactive with the isocyanate functions; a second component comprising across-linking agent in solution or in dispersion in water, saidcross-linking agent comprising at least one molecule having blocked ornon-blocked aliphatic isocyanate group(s) and/or at least saidencapsulated adhesion promoter (P).
 4. The laminated product as claimedin claim 3, wherein said first component and said second component areincluded in a ready-to-use monocomponent adhesive and/or primercomposition.
 5. The laminated product as claimed in claim 1, whereinsaid encapsulated adhesion promoter (P) comprises at least one aromaticorganic molecules having isocyanate groups selected from the groupconsisting of: 4,4′-methylene di(phenylisocyanate) (MDI), isophoronediisocyanate (IPDI), toluylene diisocyanate (TDI), toluylenediisocyanate-uretdione (TDI-U), TDI-urea, naphthalene-1,5-diisocyanate(NDI), 3,3′-dimethyl biphenyl-4,4′-diisocyanate (TODI) and IPDIisocyanurate (IPDI-T), and mixtures thereof.
 6. The laminated product asclaimed in claim 1, wherein said encapsulated adhesion promotercomprises at least one TDI type and/or IPDI type aromatic isocyanate. 7.The laminated product as claimed in claim 1, wherein said encapsulationcomprises at least one encapsulating agent selected from aliphaticamines and mixtures thereof.
 8. The laminated product as claimed inclaim 7, wherein said at least one encapsulating agent is selected fromthe group consisting of: 2-pentamethylene-1,5-diamine and its isomersand homologs; 1,6-hexamethylene diamine, di-sec-butylamine; ethylenediamine; 1,3-propylene diamine; diethylene triamine; triethylenetetramine; 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; methylnonanediamine; isophorone diamine; 4,4′-diaminodicyclohexylmethane; an alkanolamine; an alkanol diamine, ethanolamine, and diethanolamine.
 9. Thelaminated product as claimed in claim 1, wherein said at least one TPEis selected from copolyetheresters (COPEs) and/or thermoplasticpolyurethanes (TPUs) and/or copolymers having polyamide blocks andpolyether blocks (PEBAs) and/or mixtures thereof.
 10. The laminatedproduct as claimed in claim 1, wherein the material of substrate S1 andthe material of substrate S2 have the same chemical nature.
 11. Thelaminated product as claimed in claim 1, wherein the material ofsubstrate S1 and the material of substrate S2 have different natures, S2being selected from the group consisting of TPEs, homopolymers andcopolymers; polyolefins; polyamines; polyamides; polyesters; polyethers;polyesterethers; polyimides; polycarbonates; phenolic resins;polyurethanes, cross-linked or not cross-linked; poly(ethylene-vinylacetate); natural or synthetic elastomers; polybutadienes,polyisoprenes, styrene-butadiene-styrenes (SBS),styrene-butadiene-aerylonitriles (SBN), polyacrylonitriles; natural orsynthetic fabrics; fabrics formed from polypropylene, polyethylene,polyesters, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride orpolyamide fibers; fabrics formed from glass fibers or carbon fibers,leather, paper or card; and mixtures thereof.
 12. A method forassembling two substrates S1 and S2 by bonding by means of an aqueousadhesive joint, at least one of said substrates being formed from(TPE-PA) material comprising at least one thermoplastic elastomer (TPE),and/or at least one polyamide (PA), said method comprising the followingorder of steps: (a) cleaning the surface of the (TPE-PA) substrate orsubstrates with a cleaning solution; (b) applying an aqueous adhesivejoint comprising an adhesion promoter comprising at least one organicmolecule comprising at least two isocyanate functions block byencapsulation of said organic molecule to said surface of at least oneof the two substrates; (c) curing the adhesive joint at a temperature inthe range 60° C. to 150° C.; (d) bringing said surface comprising theaqueous adhesive joint of one of the substrates into contact with asurface of the other substrate to form an assembly comprising the twosubstrates with the aqueous adhesive joint between them; (e) placing theassembly in a press; (f) removing the assembly from the press in theform of a laminated product.
 13. The method as claimed in claim 12,wherein step (b) for applying said adhesive joint comprises: applying alayer of primer comprising an adhesion promoter P based on anencapsulated highly reactive aromatic isocyanate; applying a layer ofbicomponent adhesive based on a low reactivity non-blocked aliphaticisocyanate.
 14. (canceled)
 15. An aqueous adhesion promoting adhesivejoint for bonding a surface of a first substrate (S1) to a surface of asecond substrate (S2), at least one of said substrates comprising amaterial (TPE-PA) comprising at least one thermoplastic elastomer (TPE)and/or at least one polyamide (PA), said adhesive joint comprising anencapsulated adhesion promoter as defined in any one of claims 1 to 11.16. The laminated product as claimed in claim 1, wherein said at leastone TPE/PA substrate comprises at least one material formed fromamorphous or quasi-amorphous TPE and/or amorphous or quasi-amorphouspolyamide.
 17. The laminated product as claimed in claim 16, whereinsaid material has an amorphous or quasi-amorphous TPE and/or amorphousor quasi-amorphous polyamide content representing 5% to 70% by weight ofthe total material weight.
 18. The laminated product as claimed in claim16, wherein said at least one amorphous or quasi-amorphous TPE isselected from: amorphous or quasi-amorphous COPEs and/or amorphous orquasi-amorphous TPUs and/or amorphous or quasi-amorphous PEBAs.
 19. Thelaminated product as claimed in claim 2, wherein said encapsulatedadhesion promoter (P) is used in said aqueous primer and/or said aqueousadhesive such that the quantity of adhesion promoter (P) represents 0.5%to 10% by weight of active substance with respect to the total adhesivejoint weight.